Several ways to synthesize solvated and desolvated calcium tetrahydroaluminate by wet-chemical and mechanochemical methods are presented. The products were characterized by elemental analysis, X-ray diffraction (XRD), and infrared spectroscopy (FTIR). The crystal structure of Ca(AlH(4))(2).4THF was determined. After desolvation, an ultrafine powder was obtained. IR data and the mass balance suggest a compound with the composition Ca(AlH(4))(2), containing tetrahedral [AlH(4)] groups.